Balaure Paul Catalin, Grumezescu Alexandru Mihai
University "Politehnica" of Bucharest, Faculty of Applied Chemistry and Material Science, Department of Science and Engineering of Oxide Materials and Nanomaterials, G. Polizu Street 1-7, 011061, Bucharest, Romania.
Curr Med Chem. 2014;21(29):3333-74. doi: 10.2174/0929867321666140304103437.
Smart multifunctional polymeric nanocarriers able to respond to physicochemical changes in their environment or to external stimuli represent a new paradigm in the field of pharmaceutical formulations for controlled drug delivery. The introductory part of the present review deals with this new concept and presents the main advantages resulting from the use of such nanovehicles instead of conventional, much larger drug delivery systems. The access to drug nanocarriers based on smart supramolecular polymeric materials is primarily limited by the available polymerization methods capable to produce polymers with low polydispersity index, as well as much more complex macromolecular architectures with strictly controlled chemical composition, such as block copolymers and star or graft polymers or copolymers. This article reviews the state-of-the art in controlled/"living" free radical polymerization techniques as well as ring opening polymerization methods. Nitroxide mediated free radical polymerization (NMP), atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain-transfer polymerization (RAFT), single electron transfer-living radical polymerization (SET-LRP), single electron transfer-nitroxide radical coupling reaction (SET-NRC), cationic ring opening polymerization (CROP), anionic ring opening polymerization (AROP), and metal catalyzed ring opening polymerization are described, highlighting their mechanistic details and their synthetic potential as well as their limitations. The final part of the article is dedicated to a special type of unimolecular, monodisperse nanocarriers - the dendrimers. Both divergent and convergent approaches to dendrimer synthesis are described along with the therapeutic applications taking advantage of the unique branched tree-like globular structure of dendrimers to treat cancer.
能够响应其环境中的物理化学变化或外部刺激的智能多功能聚合物纳米载体代表了用于控制药物递送的药物制剂领域的新范例。本综述的引言部分论述了这一新概念，并介绍了使用此类纳米载体而非传统的、大得多的药物递送系统所带来的主要优势。基于智能超分子聚合物材料的药物纳米载体的获取主要受限于能够生产具有低多分散指数的聚合物以及具有严格控制的化学组成的更为复杂的大分子结构（如嵌段共聚物、星形或接枝聚合物或共聚物）的可用聚合方法。本文综述了可控/“活性”自由基聚合技术以及开环聚合方法的研究现状。描述了氮氧自由基介导的自由基聚合（NMP）、原子转移自由基聚合（ATRP）、可逆加成-断裂链转移聚合（RAFT）、单电子转移-活性自由基聚合（SET-LRP）、单电子转移-氮氧自由基偶联反应（SET-NRC）、阳离子开环聚合（CROP）、阴离子开环聚合（AROP）以及金属催化的开环聚合，突出了它们的机理细节、合成潜力以及局限性。本文的最后一部分专门论述了一种特殊类型的单分子、单分散纳米载体——树枝状大分子。描述了树枝状大分子合成的发散法和收敛法，以及利用树枝状大分子独特的分支树状球状结构治疗癌症的治疗应用。
